Pyridine compounds which have useful insecticidal utility

ABSTRACT

The present invention relates to a compound having the formula below which has an excellent inseciticidal activity: ##STR1## wherein R 1  represents an optionally substituted 5-6 membered aromatic hetero ring containing nitrogen atom, except a non-substituted 2-pyridyl; x represents an optionally substituted C 1-3  alkylene 
     R 2  represents a hydrogen, a carbamoyl, a mono or di C 1-5  alkyl carbamoyl, a thiocarbamoyl, a mono or di C 1-5  alkylthiocarbamoyl, a sulfamoyl, a mono or di C 1-5  alkylsulfamoyl, an optionally substituted C 1-5  alkyl, an optionally substituted C 2-5  alkenyl, an optionally substituted C 2-5  alkynyl, an optionally substituted C 3-8  cycloalkyl, an optionally substituted C 3-8  cycloalkenyl, an optionally substituted aryl or --Y--R 5  ; 
     Y represents O, S(O) n , CO, CS or CO 2  ; 
     n represents 0, 1 or 2; 
     R 5  represents a hydrogen, an optionally substituted C 1-5  alkyl, an optionally substituted C 2-5  alkenyl, an optionally substituted C 2-5  alkynyl, an optionally substituted C 3-8  cycloalkyl, an optionally substituted C 3-8  cycloalkenyl or an optionally substituted aryl; 
     R 3  represents a hydrogen, an optionally substituted C 1-5  alkyl, an optionally substituted C 2-5  alkenyl, an optionally substituted C 2-5  alkynyl, an optionally substituted C 3-8  cycloalkyl or an optionally substituted C 3-8  cycloalkenyl; R 4  represents a cyano or a nitro; and Z represents CH or N; or its salt.

FIELD OF INVENTION

The present invention relates to new amine derivatives, the processesfor the production thereof and insecticides containing the saidderivatives as effective compounds.

DESCRIPTION OF RELATED ART

A large number of chemicals, for example, organophosphorus compoundssuch as parathion and malathion and carbamate compounds such as carbaryland methomyl, have been developed and put to practical use asinsecticides over many years. These insecticides have played a verygreat role for the improvement of agricultural production. However, inrecent years some of these insecticides are regulated on their usebecause of problems such as environmental pollution due to residue oraccumulation, or cause infestation of resistant insect pests as a resultof long-term use. Therefore, there is a need to develop new chemicalswhich have excellent insecticidal characteristics over various types ofinsect pests including these resistant insect pests and which can beused safely.

The following compound is known as the isomer compound of thisinvention, which has no insecticidal activity. ##STR2## Further, thefollowing compound is described in U.S. Pat. No. 4,918,088, which hasinsecticidal activities. ##STR3## The compound however shows noinsecticidal activity against lepidopterous insects and green riceleafhopper which are more serious pests on crops, though it shows someactivity against cotton aphid.

The purpose of this invention is to provide agricultural chemicals whichcan be advantageously synthesized industrially, have certain effects andmay be applied safely.

The compound of this invention has high insecticidal activity againstboth lepidopterous and hemipterous insects.

SUMMARY OF THE INVENTION

The present invention relates to a compound having the formula ##STR4##wherein R₁ represents an optionally substituted 5-6 membered aromatichetero ring containing nitrogen atom, except a nonsubstituted 2-pyridyl;

X represents an optionally substituted C₁₋₃ alkylene or alkylidene;

R₂ represents a hydrogen, a carbamoyl, a mono or di C₁₋₅ alkylcarbamoyl, a thiocarbamoyl, a mono or di C₁₋₅ alkylthiocarbamoyl, asulfamoyl, a mono or di C₁₋₅ alkylsulfamoyl, an optionally substitutedC₁₋₅ alkyl, an optionally substituted C₂₋₅ alkenyl, an optionallysubstituted C₂₋₅ alkynyl, an optionally substituted C₃₋₈ cycloalkyl, anoptionally substituted C₃₋₈ cycloalkenyl, an optionally substituted arylor --Y--R₅ ;

Y represents O, S(O)_(n), CO, CS or CO₂ ;

n represents 0, 1 or 2;

R₅ represents a hydrogen, an optionally substituted C₁₋₅ alkyl, anoptionally substituted C₂₋₅ alkenyl, an optionally substituted C₂₋₅alkynyl, an optionally substituted C₃₋₈ cycloalkyl, an optionallysubstituted C₃₋₈ cycloalkenyl or an optionally substituted aryl;

R₃ represents a hydrogen, an optionally substituted C₁₋₅ alkyl, anoptionally substituted C₂₋₅ alkenyl, an optionally substituted C₂₋₅alkynyl, an optionally substituted C₃₋₈ cycloalkyl or an optionallysubstituted C₃₋₈ cycloalkenyl;

R₄ represents a cyano or a nitro; and Z represents CH or N; or its salt.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The compounds of this invention can be prepared in accordance with thefollowing reaction schemes:

(1) Preparation Method 1: ##STR5## where r¹ and r² represent a C₁₋₅alkyl; and R₁, R₂, R₃, R₄ and X are as defined above.

The reaction is carried out in an inactive organic solvent, preferablyin an aromatic hydrocarbon solvent such as xylene, toluene or benzene,in the presence of acidic catalyst such as p-toluenesulfonic acid, ifnecessary, under reflux.

(2) Preparation method 2: ##STR6## where r³ represents a C₁₋₅ alkyl: andR₁, R₂, R₃ and X are as defined above. This reaction is carried out inan inactive organic solvent, preferably in an alcohol such as methanol,ethanol, between room temperature and the boiling point of the usedsolvent.

(3) Preparation Method 3: ##STR7## where Hal represents a halogen; andR₁, R₂, R₃ and X are as defined above. This reaction is carried out inan inactive organic solvent, preferably DMF, THF, benzene acetonitrile,acetone, methylethylketone, in the presence of acid accepter such aspotassium carbonate, NaH, triethylamine, between room temperature andthe boiling point of the used solvent.

(4) Preparation Method 4: ##STR8## where R₁, R₂, R₃, X and Hal are asdefined above. This reaction is carried out in the same manner as thatof Preparation Method 3.

(5) Preparation Method 5: ##STR9## where R₁, R₂, R₃ and X are as definedabove. This reaction is carried out in an inactive organic solvent,preferably acetonitrile, carbon tetrachloride, dichloroethane, in thepresence of nitration reagent such as nitronium tetrafluoroborate,between -20° C. and the boiling point of the used solvent.

After the reaction is completed, an usual after-treatment gives theintended compound. The structure of the compounds of this invention wasdetermined by such means as IR, NMR, MASS, etc. When R₂ is hydrogen in acompound of this invention, tautomers represented by ##STR10## canexist.

The syn-aniti isomers, when Z represents N, and the cis-trans isomers,when Z represents CH, as represented by, ##STR11## can also exist.

The ratio varies depending on e.g. conditions of instrumental analysis.

The following EXAMPLES illustrate the present invention.

EXAMPLE 1 2-(2-chloro-5-pyridylmethylamino)-1-nitro-1-butene ##STR12##

In 50 ml of toluene, 4.2 g of 2-chloro-5-pyridylmethylamine, 3.5 g of1-nitro-2-butanone and 0.1 g of p-toluene sulfonic acid were mixed andthe mixture was refluxed for 2 hours. The solvent was then distilled offand the residue was purified by column chromatography on silica gel toafford 4.1 g of compound No. 368. m.p. 95°-98° C.

EXAMPLE 2 2-(2-chloro-5-pyridylmethylamino)-1-cyano-1-propene ##STR13##

1.4 g of 2-chloro-5-pyridylmethylamine and 0.8 g of 1-cyano-2-propanonewere mixed and the mixture was stirred at room temperature over night.The solvent was then distilled off and the residue was purified bycolumn chromatography on silica gel to afford 1.7 g of compound No. 528.m.p. 95°-98° C.

EXAMPLE 3 N-cyano-N'-(2-chloro-5-pyridylmethyl)-N'-methylacetamidine##STR14##

In 20 ml of ethanol, 1.6 g of N-methyl-2-cloro-5-pyridylmethylamine and1.2 g of ethyl-N-cyanoacetamidine were mixed and the mixture was stirredat room temperature over night. The solvent was then distilled off andthe residue was purified by column chromatography on silica gel toafford 1.8 g of compound No. 22. m.p. 101°-103° C.

EXAMPLE 4 N-cyano-N'-(2-chloro-5-pyridylmethyl)-N'-ethylacetamidine##STR15##

0.7 g of sodium hydride (purity 60%) was added to the solution of 3.0 gof N-cyano-N'-(2-chloro-5-pyridylmethyl)acetamidine in 20 ml ofN.N-dimethylformamide at ice bath temperature. After stirring it at thesame temperature for 1 hour, 2.7 g of ethyl iodide was added to themixture, followed by stirring for 5 hours at room temperature. Thereaction mixture was then poured into ice-water, extracted with ethylacetate, dried over anhydrous magnesium sulfate and concentrated underreduced pressure. The residue obtained was purified by columnchromatography on silica gel to afford 1.6 g of compound No. 51. m.p.100°-101° C.

EXAMPLE 5 N-cyano-N-(2-chloro-5-pyridylmethyl)-N'-methylacetamidine##STR16##

0.6 g of sodium hydride (purity 60%) was added to the solution of 1.3 gof N-cyano-N'-methylacetamidine in 20 ml of N,N-dimethylformamide at icebath temperature. After stirring it at the same temperature for 1 hour,2.2 g of 2-chloro-5-pyridylmethylchloride was added to the mixture,followed by stirring for 5 hours at room temperature. The reactionmixture was then poured into ice-water, extracted with ethyl acetate,dried over anhydrous magnesium sulfate and concentrated under reducedpressure. The residue obtained was purified by column chromatography onsilica gel to afford 1.5 g of compound No. 22 m.p. 101°-103° C.

REFERENCE EXAMPLE N-(2-chloro-5-pyridylmethyl)-N-methylacetamidinehydrochloride ##STR17##

To 40 ml of ethanol was added 5.1 g ofN-(2-chloro-5-pyridylmethyl)-N-Methylamine and then 4 g of ethylacetimidate hydrochloride at 0° C. After stirring for an hour, thereaction mixture was allowed to warm to room temperature and stirredover night. The solvent was then distilled off. The obtained whiteresidue was washed with diethyl ether to afford 7.3 g of the titlecompound m.p. 192°-197° C.

EXAMPLE 6 N-(2-chloro-5-pyridylmethyl)-N-methyl-N'-nitroacetamidine##STR18##

To a suspension of 1 g of N-(2-chloro-5-pyridylmethyl)-N-methylamidinehydrochloride in 10 ml of dry acetonitrile was added dropwise 0.7 g ofDBU under nitrogen at room temperature. After stirring for 30 minutes,the solution was added dropwise to a suspension of 0.6 g of nitroniumtetrafluoroborate in 5 ml of dry acetonitrile under nitrogen on coolingwith ice-water and let stir for 4 hours. After which time, the mixturewas poured into ice-water, then extracted several time with chloroform.The combined chloroform layer was dried over magnesium sulfate, filteredand distilled off. The crude oil was purified by column chromatgraphy onsilica gel to afford 0.3 g of compound No. 236.

N_(D) ²⁵ 1.5808.

Typical examples of this invention including those described above arelisted in Table 1.

                                      TABLE 1                                     __________________________________________________________________________     poundCom-                                                                         ##STR19##                                             [ ]pertiesPro-P                                                              hysical             No.                                                                              R.sub.1 X         R.sub.2      R.sub.3           Z  R.sub.4                                                                          m.p.                __________________________________________________________________________                                                              °C.           1                                                                                ##STR20##        H            H                 N  CN [123-126]            2 "                 "            CH.sub.3          "  "  [141-143]            3 "                 "            CH.sub.2 Cl       "  "  [124-126]            4 "                 "            CH.sub.2 F        "  "  [151-152]            5 "                 "            CF.sub.3          "  "  [112-114]            6 "                 "            C.sub.2 H.sub.5   "  "  [120-122]            7 "                 "            C.sub.3 H.sub.7 (n)                                                                             "  "  [100-101]            8 "                 "                                                                                           ##STR21##        "  "  [193.5- 195]         9 "                 "            C.sub.4 H.sub.9 (t)                                                                             "  "                       10                                                                              "                 "            CH.sub.2 OCH.sub.3                                                                              "  "  [128-                                                                         128.5]               11                                                                              "                 "            CH.sub.2 SCH.sub.3                                                                              "  "  [116-118]            12                                                                               ##STR22##        H            CH.sub.2 COOC.sub.2 H.sub.5                                                                     N  CN n.sub.D.sup.25.5                                                               1.5608              13                                                                              "                 "            CH.sub.2 CH.sub.2 COOC.sub.2 H.sub.5                                                            "  "                       14                                                                              "                 "            CH.sub.2 NHCH.sub.3                                                                             "  "                       15                                                                              "                 "            CH.sub.2 N(CH.sub.3).sub.2                                                                      "  "                       16                                                                              "                 "            CH.sub.2 CH.sub.2 CH.sub.2 Cl                                                                   "  "  [114-115]            17                                                                              "                 "                                                                                           ##STR23##        "  "  [190-191]            18                                                                              "                 "            CH.sub.2 CN       "  "  [106-108]            19                                                                              "                 "            CH.sub.2 CH.sub.2 CN                                                                            "  "                       20                                                                              "                 "                                                                                           ##STR24##        "  "  [187-189]            21                                                                              "                 CH.sub.3     H                 "  "  n.sub.D.sup.25                                                                1.5918               22                                                                              "                 "            CH.sub.3          "  "  [101-103]            23                                                                              "                 "            "                 "  "  [161-162]                                                                     HCl salt             24                                                                              "                 "            CH.sub.2 Cl       "  "  n.sub.D.sup.26.5                                                              .                                                                             1.5921               25                                                                              "                 "            CH.sub.2 F        "  "  [79-80]              26                                                                              "                 "            CF.sub.3          "  "  *1                   27                                                                               ##STR25##        CH.sub.3     C.sub.2 H.sub.5   N  CN n.sub.D.sup.27                                                                1.5742               28                                                                              "                 "            C.sub.3 H.sub.7 (n)                                                                             "  "  [97-100]             29                                                                              "                 "                                                                                           ##STR26##        "  "  n.sub.D.sup.24.5                                                               1.5829              30                                                                              "                 "            C.sub.4 H.sub.9 (t)                                                                             "  "                       31                                                                              "                 "            CH.sub.2 OCH.sub.3                                                                              "  "  n.sub.D.sup.24                                                                1.5803               32                                                                              "                 "            CH.sub.2 SCH.sub.3                                                                              "  "  n.sub.D.sup.24.5                                                              1.6070               33                                                                              "                 "            CH.sub.2 COOC.sub.2 H.sub.5                                                                     "  "  n.sub.D.sup.25.5                                                              1.5604               34                                                                              "                 "            CH.sub.2 CH.sub. 2 COOC.sub.2 H.sub.5                                                           "  "  n.sub.D.sup.24.5                                                              1.5605               35                                                                              "                 "            CH.sub.2 NHCH.sub.3                                                                             "  "  n.sub.D.sup.25                                                                1.5861               36                                                                              "                 "            CH.sub.2 N(CH.sub.3).sub.2                                                                      "  "  n.sub.D.sup.25                                                                1.5577               37                                                                              "                 "            CH.sub.2 CH.sub.2 Cl                                                                            "  "                       38                                                                              "                 "            CH.sub.2 CH.sub.2 CH.sub.2 Cl                                                                   "  "  n.sub.D.sup.25.5                                                              1.5830               39                                                                              "                 "                                                                                           ##STR27##        "  "                       40                                                                              "                 "                                                                                           ##STR28##        "  "                       41                                                                              "                 "                                                                                           ##STR29##        "  "  n.sub.D.sup.25.5                                                               1.6040              42                                                                               ##STR30##        CH.sub.3     CHCH.sub. 2       N  CN                      43                                                                              "                 "            CH.sub.2 CN       "  "  n.sub.D.sup.25                                                                1.5913               44                                                                              "                 "            CH.sub.2 CH.sub.2 CN                                                                            "  "  [112-114]            45                                                                              "                 "                                                                                           ##STR31##        "  "                       46                                                                              "                 "                                                                                           ##STR32##        "  "  [224-226]            47                                                                              "                 CHF.sub.2    H                 "  "                       48                                                                              "                 "            CH.sub.3          "  "  n.sub.D.sup.24.5                                                              1.5423               49                                                                              "                 "            C.sub.2 H.sub.5   "  "                       50                                                                              "                 C.sub.2 H.sub.5                                                                            H                 "  "  [101-103]            51                                                                              "                 "            CH.sub.3          "  "  [100-101]            52                                                                              "                 "            C.sub. 2 H.sub.5  "  "                       53                                                                              "                 C.sub.3 H.sub.7 (i)                                                                        H                 "  "  [205-207]            54                                                                              "                 "            CH.sub.3          "  "                       55                                                                              "                 "            C.sub.2 H.sub.5   "  "                       56                                                                              "                                                                                                ##STR33##   H                 "  "                       57                                                                               ##STR34##                                                                                       ##STR35##   CH.sub.3          N  CN n.sub.D.sup.25                                                                1.5825               58                                                                              "                 "            C.sub.2 H.sub.5   "  "                       59                                                                              "                 CH.sub.2 OCH.sub.3                                                                         H                 "  "                       60                                                                              "                 "            CH.sub.3          "  "  n.sub.D.sup.25.5                                                              1.5711               61                                                                              "                 CH.sub.2 SCH.sub.3                                                                         H                 "  "                       62                                                                              "                 "            CH.sub.3          "  "  n.sub.D.sup.25                                                                1.5828               63                                                                              "                 CH.sub.2 COOC.sub.2 H.sub.5                                                                H                 "  "                       64                                                                              "                 "            CH.sub.3          "  "  n.sub.D.sup.25                                                                1.5475               65                                                                              "                                                                                                ##STR36##   H                 "  "                       66                                                                              "                 "            CH.sub.3          "  "  n.sub.D.sup.25.5                                                              1.5928               67                                                                              "                                                                                                ##STR37##   H                 "  "                       68                                                                              "                 "            CH.sub.3          "  "  n.sub.D.sup.25.5                                                              1.6155               69                                                                              "                                                                                                ##STR38##   H                 "  "                       70                                                                              "                 "            CH.sub.3          "  "  n.sub.D.sup.24.5                                                              1.6093               71                                                                              "                                                                                                ##STR39##   H                 "  "                       72                                                                               ##STR40##                                                                                       ##STR41##   CH.sub.3          N  CN [112-114]            73                                                                              "                 CH.sub.2 CHCH.sub.2                                                                        H                 "  "  n.sub.D.sup.25                                                                1.5841               74                                                                              "                 "            CH.sub.3          "  "  n.sub.D.sup.25                                                                1.5809               75                                                                              "                 CH.sub.2 CCH H                 "  "                       76                                                                              "                 "            CH.sub.3          "  "  n.sub.D.sup.25.5                                                              1.5730               77                                                                              "                 CH.sub.2 CN  H                 "  "                       78                                                                              "                 "            CH.sub.3          "  "  [127-128]            79                                                                              "                                                                                                ##STR42##   H                 "  "                       80                                                                              "                 "            CH.sub.3          "  "  [124-127]            81                                                                              "                                                                                                ##STR43##   H                 "  "                       82                                                                              "                 "            CH.sub.3          "  "  n.sub.D.sup.24.5                                                              1.6045               83                                                                              "                                                                                                ##STR44##   H                 "  "                       84                                                                              "                 "            CH.sub.3          "  "  n.sub.D.sup.25.5                                                              1.6092               85                                                                              "                                                                                                ##STR45##   H                 "  "                       86                                                                               ##STR46##                                                                                       ##STR47##   CH.sub.3          N  CN n.sub.D.sup.25.5                                                               1.5910              87                                                                              "                                                                                                ##STR48##   H                 "  "                       88                                                                              "                 "            CH.sub.3          "  "  n.sub.D.sup.25.5                                                              1.6162               89                                                                              "                                                                                                ##STR49##   H                 "  "                       90                                                                              "                 "            CH.sub. 3         "  "  [115-117]            91                                                                              "                 OCH.sub.3    H                 "  "                       92                                                                              "                 "            CH.sub.3          "  "  [110-112]            93                                                                              "                 CHO          H                 "  "                       94                                                                              "                 "            CH.sub.3          "  "                       95                                                                              COCH.sub.3        H            "                 "  "  n.sub.D.sup.25.5                                                              1.5475               96                                                                              "                 "            CH.sub.3          "  "  [84-86]              97                                                                              "                 SO.sub.2 CH.sub.3                                                                          H                 "  "  [160-163]            98                                                                              "                 "            CH.sub.3          "  "                       99                                                                              "                                                                                                ##STR50##   H                 "  "                      100                                                                              "                 "            CH.sub.3          "  "  [112-114]           101                                                                               ##STR51##        COOC.sub.2 H.sub.5                                                                         H                 N  CN                     102                                                                              "                 "            CH.sub.3          "  "  n.sub.D.sup.25                                                                1.5540              103                                                                              "                 CONH.sub.2   H                 "  "                      104                                                                              "                 "            CH.sub.3          "  "                      105                                                                              "                                                                                                ##STR52##   H                 "  "                      106                                                                              "                 "            CH.sub.3          "  "  [89-91]             107                                                                              "                 CONHCH.sub.3 H                 "  "                      108                                                                              "                 "            CH.sub.3          "  "                      109                                                                              "                 CSNHCH.sub.3 H                 "  "                      110                                                                              "                 "            CH.sub.3          "  "                      111                                                                               ##STR53##        H            CH.sub.3          "  "                      112                                                                              "                 CH.sub.3     "                 "  "                      113                                                                               ##STR54##        H            "                 "  "                      114                                                                              "                 CH.sub.3     "                 "  "                      115                                                                               ##STR55##        H            "                 "  "  [83-85]             116                                                                               ##STR56##        CH.sub.3     CH.sub.3          N  CN [76-78]             117                                                                               ##STR57##        H            "                 "  "                      118                                                                              "                 CH.sub.3     "                 "  "  [145-147]           119                                                                               ##STR58##        H            "                 "  "                      120                                                                              "                 CH.sub.3     "                 "  "  n.sub.D.sup.25                                                                1.5202              121                                                                               ##STR59##        H            "                 "  "                      122                                                                              "                 CH.sub.3     "                 "  "                      123                                                                               ##STR60##        H            "                 "  "                      124                                                                              "                 CH.sub.3     "                 "  "  n.sub.D.sup.25.5                                                              1.5580              125                                                                               ##STR61##        H            "                 "  "                      126                                                                              "                 CH.sub.3     "                 "  "                      127                                                                               ##STR62##        H            "                 "  "                      128                                                                              "                 CH.sub.3     "                 "  "                      129                                                                               ##STR63##        H            "                 "  "  [162-163]           130                                                                              "                 CH.sub.3     "                 "  "  [105-107]           131                                                                               ##STR64##        H            CH.sub.3          N  CN                     132                                                                              "                 CH.sub.3     "                 "  "  [138-139]           133                                                                               ##STR65##        H            "                 "  "                      134                                                                              "                 CH.sub.3     "                 "  "  n.sub.D.sup.25                                                                1.5841              135                                                                               ##STR66##        H            "                 "  "                      136                                                                              "                 CH.sub.3     "                 "  "  [107-109]           137                                                                               ##STR67##        H            "                 "  "                      138                                                                              "                 CH.sub.3     "                 "  "                      139                                                                               ##STR68##        H            "                 "  "                      140                                                                              "                 CH.sub.3     "                 "  "                      141                                                                               ##STR69##        H            "                 "  "                      142                                                                              "                 CH.sub.3     "                 "  "                      143                                                                               ##STR70##        H            "                 "  "  [122-124]           144                                                                              "                 CH.sub.3     "                 "  "  [110-113]           145                                                                               ##STR71##        H            CH.sub.3          N  CN [66-68]             146                                                                              "                 CH.sub.3     "                 "  "  n.sub.D.sup.24.5                                                              1.5790              147                                                                               ##STR72##        H            "                 "  "                      148                                                                              "                 CH.sub.3     "                 "  "  [94-96]             149                                                                               ##STR73##        H            "                 "  "  [130-132]           150                                                                              "                 CH.sub.3     "                 "  "  n.sub.D.sup.                                                                  25                                                                            1.5612              151                                                                               ##STR74##        H            "                 "  "  [96-99]             152                                                                              "                 CH.sub.3     "                 "  "  n.sub.D.sup.25.5                                                              1.5800              153                                                                               ##STR75##        H            "                 "  "                      154                                                                              "                 CH.sub.3     "                 "  "                      155                                                                               ##STR76##        H            "                 "  "                      156                                                                               ##STR77##        CH.sub.3     CH.sub.3          N  CN                     157                                                                               ##STR78##        H            "                 "  "                      158                                                                              "                 CH.sub.3     "                 "  "                      159                                                                               ##STR79##        H            "                 "  "                      160                                                                              "                 CH.sub.3     "                 "  "                      161                                                                               ##STR80##        H            "                 "  "                      162                                                                              "                 CH.sub.3     "                 "  "                      163                                                                               ##STR81##        H            "                 "  "  [115-117]           164                                                                              "                 CH.sub.3     "                 "  "  n.sub.D.sup.23                                                                1.5717              165                                                                               ##STR82##        H            "                 "  "  [104-106]           166                                                                              "                 CH.sub.3     "                 "  "                      167                                                                               ##STR83##        H            CH.sub.3          N  CN                     168                                                                              "                 CH.sub.3     "                 "  "                      169                                                                               ##STR84##        H            "                 "  "  [112-114]           170                                                                              "                 CH.sub.3     "                 "  "  n.sub.D.sup.25                                                                1.5413              171                                                                               ##STR85##        H            "                 "  "  [122-124]           172                                                                              "                 CH.sub.3     "                 "  "  [143-144]           173                                                                              "                 "            C.sub.2 H.sub.5   "  "  n.sub.D.sup.25                                                                1.5575              174                                                                              "                 C.sub.2 H.sub.5                                                                            CH.sub.3          "  "  [63-70]             175                                                                               ##STR86##        H            "                 "  "  [149-151]           176                                                                              "                 CH.sub.3     "                 "  "                      177                                                                               ##STR87##        H            H                 "  "  [179-183]           178                                                                              "                 CH.sub.3     "                 "  "  n.sub.D.sup.25                                                                1.5952              179                                                                               ##STR88##        H            CH.sub.3          N  CN                     180                                                                              "                 CH.sub.3     "                 "  "                      181                                                                               ##STR89##        H            "                 "  "                      182                                                                              "                 CH.sub.3     "                 "  "                      183                                                                               ##STR90##        H            "                 "  "                      184                                                                              "                 CH.sub.3     "                 "  "                      185                                                                               ##STR91##        H            "                 "  "                      186                                                                              "                 CH.sub.3     "                 "  "                      187                                                                               ##STR92##        H            "                 "  "                      188                                                                              "                 CH.sub.3     "                 "  "  [106-109]           189                                                                               ##STR93##        H            CH.sub.3          "  "  [90-92]             190                                                                               ##STR94##        CH.sub.3     CH.sub.3          N  CN [102-103]           191                                                                               ##STR95##        H            "                 "  "                      192                                                                              "                 CH.sub.3     "                 "  "                      193                                                                               ##STR96##        H            H                 "  "                      194                                                                              "                 "            CH.sub.3          "  "  [127-129]           195                                                                              "                 "            CH.sub.2 Cl       "  "                      196                                                                              "                 "            CH.sub.2 F        "  "                      197                                                                              "                 "            C.sub.2 H.sub.5   "  "                      198                                                                              "                 "                                                                                           ##STR97##        "  "                      199                                                                              "                 "            CH.sub.2 SCH.sub.3                                                                              "  "                      200                                                                              "                 "            CH.sub.2 OCH.sub.3                                                                              "  "                      201                                                                               ##STR98##        H            C.sub.3 H.sub.7 (n)                                                                             N  CN n.sub.D.sup.25.5                                                               1.5528             202                                                                              "                 CH.sub.3     H                 "  "                      203                                                                              "                 "            CH.sub.3          "  "  n.sub.D.sup.25.5                                                              1.5798              204                                                                              "                 "            CH.sub.2 Cl       "  "                      205                                                                              "                 "            CH.sub.2 F        "  "                      206                                                                              "                 H            C.sub.2 H.sub.5   "  "  n.sub.D.sup.25.5                                                              1.5657              207                                                                              "                 "                                                                                           ##STR99##        "  "                      208                                                                              "                 "            CH.sub.2 SCH.sub.3                                                                              "  "                      209                                                                              "                 "            CH.sub.2 OCH.sub.3                                                                              "  "                      210                                                                              "                 "            C.sub.3 H.sub.7 (i)                                                                             "  "                      211                                                                              "                 "            C.sub.4 H.sub.9 (t)                                                                             "  "                      212                                                                               ##STR100##       C.sub.2 H.sub.5                                                                            H                 N  CN                     213                                                                              "                 "            CH.sub.3          "  "  n.sub.D.sup.24.5                                                              1.5665              214                                                                              "                 "            CH.sub.2 Cl       "  "                      215                                                                              "                 "            C.sub.2 H.sub.5   "  "                      216                                                                              "                 C.sub.3 H.sub.7 (i)                                                                        H                 "  "                      217                                                                              "                 "            CH.sub.3          "  "                      218                                                                              "                 "            C.sub.2 H.sub.5   "  "                      219                                                                              "                 COCH.sub.3   H                 "  "                      220                                                                              "                 "            CH.sub.3          "  "                      221                                                                              "                 SO.sub.2 CH.sub.3                                                                          H                 "  "                      222                                                                              "                 "            CH.sub.3          "  "                      223                                                                               ##STR101##       H            H                 N  NO.sub.2               224                                                                              "                 "            CH.sub.3          "  "                      225                                                                              "                 "            CH.sub.2 Cl       "  "                      226                                                                              "                 "            CH.sub.2 F        "  "                      227                                                                              "                 "            C.sub.2 H.sub.5   "  "                      228                                                                              "                 "                                                                                           ##STR102##       "  "                      229                                                                              "                 "            CH.sub.2 SCH.sub.3                                                                              "  "                      230                                                                              "                 "            CH.sub.2 OCH.sub.3                                                                              "  "                      231                                                                              "                 "            C.sub.3 H.sub.7 (i)                                                                             "  "                      232                                                                              "                 "            C.sub.4 H.sub.9 (t)                                                                             "  "                      233                                                                              "                 "            CHCH.sub.2        "  "                      234                                                                              "                 "                                                                                           ##STR103##       "  "                      235                                                                               ##STR104##       CH.sub.3     H                 N  NO.sub.2               236                                                                              "                 "            CH.sub.3          "  "  n.sub.D.sup.25                                                                1.5808              237                                                                              "                 "            CH.sub.2 Cl       "  "                      238                                                                              "                 "            CH.sub.2 F        "  "                      239                                                                              "                 "            C.sub.2 H.sub.5   "  "                      240                                                                              "                 "                                                                                           ##STR105##       "  "                      241                                                                              "                 "            CH.sub.2 SCH.sub.3                                                                              "  "                      242                                                                              "                 "            CH.sub.2 OCH.sub.3                                                                              "  "                      243                                                                              "                 "            C.sub.3 H.sub.7 (n)                                                                             "  "                      244                                                                              "                 "            C.sub.4 H.sub.9 (t)                                                                             "  "                      245                                                                              "                 "            CHCH.sub.2        "  "                      246                                                                              "                 "                                                                                           ##STR106##       "  "                      247                                                                               ##STR107##       C.sub.2 H.sub.5                                                                            H                 N  NO.sub.2               248                                                                              "                 "            CH.sub.3          "  "                      249                                                                              "                 "            C.sub.2 H.sub.5   "  "                      250                                                                              "                 C.sub.3 H.sub.7 (i)                                                                        H                 "  "                      251                                                                              "                 "            CH.sub.3          "  "                      252                                                                              "                 "            C.sub.2 H.sub.5   "  "                      253                                                                              "                                                                                                ##STR108##  H                 "  "                      254                                                                              "                 "            CH.sub.3          "  "                      255                                                                              "                 "            C.sub.2 H.sub.5   "  "                      256                                                                              "                 COCH.sub.3   H                 "  "                      257                                                                              "                 "            CH.sub.3          "  "                      258                                                                              "                 SO.sub.2 CH.sub.3                                                                          H                 "  "                      259                                                                              "                 "            CH.sub.3          "  "                      260                                                                               ##STR109##       H            CH.sub.3          N  NO.sub.2               261                                                                              "                 CH.sub.3     "                 "  "                      262                                                                               ##STR110##       H            "                 "  "                      263                                                                              "                 CH.sub.3     "                 "  "                      264                                                                               ##STR111##       H            "                 "  "                      265                                                                              "                 CH.sub.3     "                 "  "                      266                                                                               ##STR112##       H            "                 "  "                      267                                                                              "                 CH.sub.3     "                 "  "                      268                                                                               ##STR113##       H            "                 "  "                      269                                                                              "                 CH.sub.3     "                 "  "                      270                                                                               ##STR114##       H            "                 "  "                      271                                                                              "                 CH.sub.3     "                 "  "                      272                                                                               ##STR115##       H            CH.sub.3          N  NO.sub.2               273                                                                              "                 CH.sub.3     "                 "  "                      274                                                                               ##STR116##       H            "                 "  "                      275                                                                              "                 CH.sub.3     "                 "  "                      276                                                                               ##STR117##       H            "                 "  "                      277                                                                              "                 CH.sub.3     "                 "  "                      278                                                                               ##STR118##       H            "                 "  "                      279                                                                              "                 CH.sub.3     "                 "  "                      280                                                                               ##STR119##       H            "                 "  "                      281                                                                              "                 CH.sub.3     "                 "  "                      282                                                                               ##STR120##       H            "                 "  "                      283                                                                              "                 CH.sub.3     "                 "  "                      284                                                                               ##STR121##       H            CH.sub.3          N  NO.sub.2               285                                                                              "                 CH.sub.3     "                 "  "                      286                                                                               ##STR122##       H            "                 "  "                      287                                                                              "                 CH.sub.3     "                 "  "                      288                                                                               ##STR123##       H            "                 "  "                      289                                                                              "                 CH.sub.3     "                 "  "                      290                                                                               ##STR124##       H            "                 "  "                      291                                                                              "                 CH.sub.3     "                 "  "                      292                                                                               ##STR125##       H            "                 "  "                      293                                                                              "                 CH.sub.3     "                 "  "                      294                                                                               ##STR126##       H            CH.sub.3          N  NO.sub.2               295                                                                              "                 CH.sub.3     "                 "  "                      296                                                                               ##STR127##       H            "                 "  "                      297                                                                              "                 CH.sub.3     "                 "  "                      298                                                                               ##STR128##       H            "                 "  "                      299                                                                              "                 CH.sub.3     "                 "  "                      300                                                                               ##STR129##       H            "                 "  "                      301                                                                              "                 CH.sub.3     "                 "  "                      302                                                                               ##STR130##       H            "                 "  "                      303                                                                              "                 CH.sub.3     "                 "  "                      304                                                                               ##STR131##       H            "                 "  "                      305                                                                               ##STR132##       CH.sub.3     CH.sub.3          N  NO.sub.2               306                                                                               ##STR133##       H            "                 "  "                      307                                                                              "                 CH.sub.3     "                 "  "                      308                                                                               ##STR134##       H            "                 "  "                      309                                                                              "                 CH.sub.3     "                 "  "                      310                                                                               ##STR135##       H            "                 "  "                      311                                                                              "                 CH.sub.3     "                 "  "                      312                                                                               ##STR136##       H            "                 "  "                      313                                                                              "                 CH.sub.3     "                 "  "                      314                                                                               ##STR137##       H            CH.sub.3          N  NO.sub.2               315                                                                              "                 CH.sub.3     "                 "  "                      316                                                                               ##STR138##       H            "                 "  "                      317                                                                              "                 CH.sub.3     "                 "  "                      318                                                                               ##STR139##       H            "                 "  "                      319                                                                              "                 CH.sub.3     "                 "  "                      320                                                                              "                 "            C.sub.2 H.sub.5   "  "                      321                                                                              "                 C.sub.2 H.sub.5                                                                            CH.sub.3          "  "                      322                                                                               ##STR140##       H            "                 "  "                      323                                                                              "                 CH.sub.3     "                 "  "                      324                                                                               ##STR141##       H            CH.sub.3          N  NO.sub.2               325                                                                              "                 CH.sub.3     "                 "  "                      326                                                                               ##STR142##       H            "                 "  "                      327                                                                              "                 CH.sub.3     "                 "  "                      328                                                                               ##STR143##       H            "                 "  "                      329                                                                              "                 CH.sub.3     "                 "  "                      330                                                                               ##STR144##       H            "                 "  "                      331                                                                              "                 CH.sub.3     "                 "  "                      332                                                                               ##STR145##       H            "                 "  "                      333                                                                              "                 CH.sub.3     "                 "  "                      334                                                                               ##STR146##       H            "                 "  "                      335                                                                              "                 CH.sub.3     "                 "  "                      336                                                                               ##STR147##       H            H                 N  NO.sub.2               337                                                                              "                 "            CH.sub.3          "  "                      338                                                                              "                 "            C.sub.2 H.sub.5   "  "                      339                                                                              "                 "            CH.sub.2 Cl       "  "                      340                                                                              "                 "            CH.sub.2 F        "  "                      341                                                                              "                 "                                                                                           ##STR148##       "  "                      342                                                                              "                 "            CH.sub.2 SCH.sub.3                                                                              "  "                      343                                                                              "                 "            CH.sub.2 OCH.sub.3                                                                              "  "                      344                                                                               ##STR149##       CH.sub.3     H                 N  NO.sub.2               345                                                                              "                 "            CH.sub.3          "  "                      346                                                                              "                 "            CH.sub.2 Cl       "  "                      347                                                                              "                 "            CH.sub.2 F        "  "                      348                                                                              "                 "            C.sub.2 H.sub.5   "  "                      349                                                                              "                 "                                                                                           ##STR150##       "  "                      350                                                                              "                 "            CH.sub.2 SCH.sub.3                                                                              "  "                      351                                                                              "                 "            CH.sub.2 OCH.sub.3                                                                              "  "                      352                                                                              "                 "            C.sub.3 H.sub.7 (i)                                                                             "  "                      353                                                                              "                 "            C.sub.4 H.sub.9 (t)                                                                             "  "                      354                                                                               ##STR151##       C.sub.2 H.sub.5                                                                            H                 N  NO.sub.2               355                                                                              "                 "            CH.sub.3          "  "                      356                                                                              "                 "            CH.sub.2 Cl       "  "                      357                                                                              "                 "            C.sub.2 H.sub.5   "  "                      358                                                                              "                 C.sub.3 H.sub.7 (i)                                                                        H                 "  "                      359                                                                              "                 "            CH.sub.3          "  "                      360                                                                              "                 "            C.sub.2 H.sub.5   "  "                      361                                                                              "                 COCH.sub.3   H                 "  "                      362                                                                              "                 "            CH.sub.3          "  "                      363                                                                              "                 SO.sub.2 CH.sub.3                                                                          H                 "  "                      364                                                                              "                 "            CH.sub.3          "  "                      365                                                                               ##STR152##       H            H                 CH NO.sub.2                                                                         [116-118]           366                                                                              "                 "            CH.sub.3          "  "  [133-135]           367                                                                              "                 "            CH.sub.2 Cl       "  "                      368                                                                              "                 "            C.sub.2 H.sub.5   "  "  [95-98]             369                                                                              "                 "            C.sub.3 H.sub.7 (i)                                                                             "  "  [150-152]           370                                                                              "                 "            C.sub.4 H.sub.7 (t)                                                                             "  "                      371                                                                              "                 "            CHCH.sub.2        "  "                      372                                                                              "                 "            CHCHCH.sub.3      "  "                      373                                                                              "                 "            CH.sub.2 CN       "  "                      374                                                                              "                 "            CH.sub.2 NO.sub.2 "  "                      375                                                                              "                 "            CH.sub.2 COOC.sub.2 H.sub.5                                                                     "  "                      376                                                                               ##STR153##       H                                                                                           ##STR154##       CH NO.sub.2               377                                                                              "                 "                                                                                           ##STR155##       "  "                      378                                                                              "                 "                                                                                           ##STR156##       "  "                      379                                                                              "                 "                                                                                           ##STR157##       "  "                      380                                                                              "                 CH.sub.3     H                 "  "                      381                                                                              "                 "            CH.sub.3          "  "  [79-82]             382                                                                              "                 "            CH.sub.2 Cl       "  "                      383                                                                              "                 "            C.sub.2 H.sub.5   "  "  [101-104]           384                                                                              "                 "            C.sub.3 H.sub.7 (i)                                                                             "  "                      385                                                                              "                 "            C.sub.4 H.sub.7 (t)                                                                             "  "                      386                                                                              "                 "            CHCH.sub.2        "  "                      387                                                                              "                 "            CHCHCH.sub.3      "  "                      388                                                                               ##STR158##       CH.sub.3     CH.sub.2 CN       CH NO.sub.2               389                                                                              "                 "            CH.sub.2 NO.sub.2 "  "                      390                                                                              "                 "            CH.sub.2 COOC.sub.2 H.sub.5                                                                     "  "                      391                                                                              "                 "                                                                                           ##STR159##       "  "                      392                                                                              "                 "                                                                                           ##STR160##       "  "                      393                                                                              "                 "                                                                                           ##STR161##       "  "                      394                                                                              "                 "                                                                                           ##STR162##       "  "                      395                                                                              "                 C.sub.2 H.sub.5                                                                            H                 "  "                      396                                                                              "                 "            CH.sub.3          "  "                      397                                                                              "                 "            C.sub.2 H.sub.5   "  "                      398                                                                              "                 C.sub.3 H.sub.7 (i)                                                                        H                 "  "                      399                                                                              "                 "            CH.sub.3          "  "                      400                                                                               ##STR163##       C.sub.3 H.sub.7 (i)                                                                        C.sub.2 H.sub.5   CH NO.sub.2               401                                                                              "                                                                                                ##STR164##  H                 "  "                      402                                                                              "                 "            CH.sub.3          "  "                      403                                                                              "                 "            C.sub.2 H.sub.5   "  "                      404                                                                              "                 CH.sub.2 CHCH.sub.2                                                                        H                 "  "                      405                                                                              "                 "            CH.sub.3          "  "                      406                                                                              "                 "            C.sub.2 H.sub.5   "  "                      407                                                                              "                                                                                                ##STR165##  H                 "  "                      408                                                                              "                 "            CH.sub.3          "  "                      409                                                                              "                 "            C.sub.2 H.sub.5   "  "                      410                                                                              "                 CHO          H                 "  "                      411                                                                              "                 "            CH.sub.3          "  "                      412                                                                               ##STR166##       CHO          C.sub.2 H.sub.5   CH NO.sub.2               413                                                                              "                 COCH.sub.3   H                 "  "                      414                                                                              "                 "            CH.sub.3          "  "                      415                                                                              "                 "            C.sub.2 H.sub.5   "  "                      416                                                                              "                 SO.sub.2 CH.sub.3                                                                          H                 "  "                      417                                                                              "                 "            CH.sub.3          "  "                      418                                                                              "                 "            C.sub.2 H.sub.5   "  "                      419                                                                              "                 COOC.sub.2 H.sub.5                                                                         H                 "  "                      420                                                                              "                 "            CH.sub.3          "  "                      421                                                                              "                 "            C.sub.2 H.sub.5   "  "                      422                                                                              "                 OC.sub.2 H.sub.5                                                                           H                 "  "                      423                                                                              "                 "            CH.sub.3          "  "                      424                                                                              "                 "            C.sub.2 H.sub.5   "  "                      425                                                                              "                 CH.sub.2 CCH H                 "  "                      426                                                                              "                 "            CH.sub.3          "  "                      427                                                                              "                 "            C.sub.2 H.sub.5   "  "                      428                                                                               ##STR167##       H            CH.sub.3          CH NO.sub.2               429                                                                              "                 CH.sub.3     "                 "  "                      430                                                                               ##STR168##       H            "                 "  "                      431                                                                              "                 CH.sub.3     "                 "  "                      432                                                                               ##STR169##       H            "                 "  "                      433                                                                              "                 CH.sub.3     "                 "  "                      434                                                                               ##STR170##       H            "                 "  "                      435                                                                              "                 CH.sub.3     "                 "  "                      436                                                                               ##STR171##       H            "                 "  "                      437                                                                              "                 CH.sub.3     "                 "  "                      438                                                                               ##STR172##       H            "                 "  "                      439                                                                              "                 CH.sub.3     "                 "  "                      440                                                                               ##STR173##       H            CH.sub.3          CH NO.sub.2               441                                                                              "                 CH.sub.3     "                 "  "                      442                                                                               ##STR174##       H            "                 "  "                      443                                                                              "                 CH.sub.3     "                 "  "                      444                                                                               ##STR175##       H            "                 "  "                      445                                                                              "                 CH.sub.3     "                 "  "                      446                                                                               ##STR176##       H            "                 "  "                      447                                                                              "                 CH.sub.3     "                 "  "                      448                                                                               ##STR177##       H            "                 "  "                      449                                                                              "                 CH.sub.3     "                 "  "                      450                                                                               ##STR178##       H            "                 "  "                      451                                                                              "                 CH.sub.3     "                 "  "                      452                                                                               ##STR179##       H            CH.sub.3          CH NO.sub.2               453                                                                              "                 CH.sub.3     "                 "  "                      454                                                                               ##STR180##       H            "                 "  "                      455                                                                              "                 CH.sub.3     "                 "  "                      456                                                                               ##STR181##       H            "                 "  "                      457                                                                              "                 CH.sub.3     "                 "  "                      458                                                                               ##STR182##       H            "                 "  "                      459                                                                              "                 CH.sub.3     "                 "  "                      460                                                                               ##STR183##       H            "                 "  "                      461                                                                              "                 CH.sub.3     "                 "  "                      462                                                                               ##STR184##       H            CH.sub.3          CH NO.sub.2               463                                                                              "                 CH.sub.3     "                 "  "                      464                                                                               ##STR185##       H            "                 "  "                      465                                                                              "                 CH.sub.3     "                 "  "                      466                                                                               ##STR186##       H            "                 "  "                      467                                                                              "                 CH.sub.3     "                 "  "                      468                                                                               ##STR187##       H            "                 "  "                      469                                                                              "                 CH.sub.3     "                 "  "                      470                                                                               ##STR188##       H            "                 "  "                      471                                                                              "                 CH.sub.3     "                 "  "                      472                                                                               ##STR189##       H            "                 "  "                      473                                                                               ##STR190##       CH.sub.3     CH.sub.3          CH NO.sub.2               474                                                                               ##STR191##       H            "                 "  "                      475                                                                              "                 CH.sub.3     "                 "  "                      476                                                                               ##STR192##       H            "                 "  "                      477                                                                              "                 CH.sub.3     "                 "  "                      478                                                                               ##STR193##       H            "                 "  "                      479                                                                              "                 CH.sub.3     "                 "  "                      480                                                                               ##STR194##       H            "                 "  "                      481                                                                              "                 CH.sub.3     "                 "  "                      482                                                                               ##STR195##       H            "                 "  "                      483                                                                              "                 CH.sub.3     "                 "  "                      484                                                                               ##STR196##       H            CH.sub.3          CH NO.sub.2               485                                                                              "                 CH.sub.3     "                 "  "                      486                                                                               ##STR197##       H            "                 "  "                      487                                                                              "                 CH.sub.3     "                 "  "                      488                                                                              "                 "            C.sub.2 H.sub.5   "  "                      489                                                                              "                 C.sub.2 H.sub.5                                                                            CH.sub.3          "  "                      490                                                                               ##STR198##       H            "                 "  "                      491                                                                              "                 CH.sub.3     "                 "  "                      492                                                                               ##STR199##       H            "                 "  "                      493                                                                              "                 CH.sub.3     "                 "  "                      494                                                                               ##STR200##       H            "                 "  "                      495                                                                              "                 CH.sub.3     "                 "  "                      496                                                                               ##STR201##       H            CH.sub.3          CH NO.sub.2               497                                                                              "                 CH.sub.3     "                 "  "                      498                                                                               ##STR202##       H            "                 "  "                      499                                                                              "                 CH.sub.3     "                 "  "                      500                                                                               ##STR203##       H            "                 "  "                      501                                                                              "                 CH.sub.3     "                 "  "                      502                                                                               ##STR204##       H            H                 CH NO.sub.2               503                                                                              "                 "            CH.sub.3          "  "                      504                                                                              "                 "            CH.sub.2 Cl       "  "                      505                                                                              "                 "            C.sub.2 H.sub.5   "  "                      506                                                                              "                 "            C.sub.3 H.sub.7 (i)                                                                             "  "                      507                                                                              "                 "            C.sub.4 H.sub.9 (t)                                                                             "  "                      508                                                                              "                 CH.sub.3     H                 "  "                      509                                                                              "                 "            CH.sub.3          "  "                      510                                                                              "                 "            CH.sub.2 Cl       "  "                      511                                                                              "                 "            C.sub.2 H.sub.5   "  "                      512                                                                              "                 "                                                                                           ##STR205##       "  "                      513                                                                               ##STR206##       CH.sub.3     C.sub.3 H.sub.7 (i)                                                                             CH NO.sub.2               514                                                                              "                 "            C.sub.4 H.sub.9 (t)                                                                             "  "                      515                                                                              "                 C.sub.2 H.sub.5                                                                            H                 "  "                      516                                                                              "                 "            CH.sub.3          "  "                      517                                                                              "                 "            C.sub.2 H.sub.5   "  "                      518                                                                              "                                                                                                ##STR207##  H                 "  "                      519                                                                              "                 "            CH.sub.3          "  "                      520                                                                              "                 "            C.sub.2 H.sub.5   "  "                      521                                                                              "                 COCH.sub.3   H                 "  "                      522                                                                              "                 "            CH.sub.3          "  "                      523                                                                              "                 "            C.sub.2 H.sub.5   "  "                      524                                                                              "                 SO.sub.2 CH.sub.3                                                                          H                 "  "                      525                                                                              "                 "            CH.sub.3          "  "                      526                                                                              "                 "            C.sub.2 H.sub.5   "  "                      527                                                                               ##STR208##       H            H                 CH CN                     528                                                                              "                 "            CH.sub.3          "  "  [95-98]             529                                                                              "                 "            CH.sub.2 Cl       "  "                      530                                                                              "                 "            C.sub.2 H.sub.5   "  "                      531                                                                              "                 "            C.sub.3 H.sub.7 (i)                                                                             "  "                      532                                                                              "                 "            C.sub.4 H.sub.9 (t)                                                                             "  "                      533                                                                              "                 "            CHCH.sub.2        "  "                      534                                                                              "                 "            CHCHCH.sub.3      "  "                      535                                                                              "                 "            CH.sub.2 CN       "  "                      536                                                                              "                 "            CH.sub.2 NO.sub.2 "  "                      537                                                                              "                 "            CH.sub.2 COOC.sub.2 H.sub.5                                                                     "  "                      538                                                                               ##STR209##       H                                                                                           ##STR210##       CH CN                     539                                                                              "                 "                                                                                           ##STR211##       "  "                      540                                                                              "                 "                                                                                           ##STR212##       "  "                      541                                                                              "                 "                                                                                           ##STR213##       "  "                      542                                                                              "                 CH.sub.3     H                 "  "                      543                                                                              "                 "            CH.sub.3          "  "  n.sub.D.sup.29                                                                1.5941              544                                                                              "                 "            CH.sub.2 Cl       "  "                      545                                                                              "                 "            C.sub.2 H.sub.5   "  "                      546                                                                              "                 "            C.sub.3 H.sub.7 (i)                                                                             "  "                      547                                                                              "                 "            C.sub.4 H.sub.9 (t)                                                                             "  "                      548                                                                              "                 "            CHCH.sub.2        "  "                      549                                                                              "                 "            CHCHCH.sub.3      "  "                      550                                                                               ##STR214##       CH.sub.3     CH.sub.2 CN       CH CN                     551                                                                              "                 "            CH.sub.2 NO.sub.2 "  "                      552                                                                              "                 "            CH.sub.2 COOC.sub.2 H.sub.5                                                                     "  "                      553                                                                              "                 "                                                                                           ##STR215##       "  "                      554                                                                              "                 "                                                                                           ##STR216##       "  "                      555                                                                              "                 "                                                                                           ##STR217##       "  "                      556                                                                              "                 "                                                                                           ##STR218##       "  "                      557                                                                              "                 C.sub.2 H.sub.5                                                                            H                 "  "                      558                                                                              "                 "            CH.sub.3          "  "                      559                                                                              "                 "            C.sub.2 H.sub.5   "  "                      560                                                                              "                 C.sub.3 H.sub.7 (i)                                                                        H                 "  "                      561                                                                              "                 "            CH.sub.3          "  "                      562                                                                               ##STR219##       C.sub.3 H.sub.7 (i)                                                                        C.sub.2 H.sub.5   CH CN                     563                                                                              "                                                                                                ##STR220##  H                 "  "                      564                                                                              "                 "            CH.sub.3          "  "                      565                                                                              "                 "            C.sub.2 H.sub.5   "  "                      566                                                                              "                 CH.sub.2 CHCH.sub.2                                                                        H                 "  "                      567                                                                              "                 "            CH.sub.3          "  "                      568                                                                              "                 "            C.sub.2 H.sub.5   "  "                      569                                                                              "                                                                                                ##STR221##  H                 "  "                      570                                                                              "                 "            CH.sub.3          "  "                      571                                                                              "                 "            C.sub.2 H.sub.5   "  "                      572                                                                              "                 CHO          H                 "  "                      573                                                                              "                 "            CH.sub.3          "  "                      574                                                                               ##STR222##       CHO          C.sub.2 H.sub.5   CH CN                     575                                                                              "                 COCH.sub.3   H                 "  "                      576                                                                              "                 "            CH.sub.3          "  "                      577                                                                              "                 "            C.sub.2 H.sub.5   "  "                      578                                                                              "                 SO.sub. 2 CH.sub.3                                                                         H                 "  "                      579                                                                              "                 "            CH.sub.3          "  "                      580                                                                              "                 "            C.sub.2 H.sub.5   "  "                      581                                                                              "                 COOC.sub.2 H.sub.5                                                                         H                 "  "                      582                                                                              "                 "            CH.sub.3          "  "                      583                                                                              "                 "            C.sub.2 H.sub.5   "  "                      584                                                                              "                 OC.sub.2 H.sub.5                                                                           H                 "  "                      585                                                                              "                 "            CH.sub.3          "  "                      586                                                                              "                 "            C.sub.2 H.sub.5   "  "                      587                                                                              "                 CH.sub.2 CCH H                 "  "                      588                                                                              "                 "            CH.sub.3          "  "                      589                                                                              "                 "            C.sub.2 H.sub.5   "  "                      590                                                                               ##STR223##       H            CH.sub.3          CH CN                     591                                                                              "                 CH.sub.3     "                 "  "                      592                                                                               ##STR224##       H            "                 "  "                      593                                                                              "                 CH.sub.3     "                 "  "                      594                                                                               ##STR225##       H            "                 "  "                      595                                                                              "                 CH.sub.3     "                 "  "                      596                                                                               ##STR226##       H            "                 "  "                      597                                                                              "                 CH.sub.3     "                 "  "                      598                                                                               ##STR227##       H            "                 "  "                      599                                                                              "                 CH.sub.3     "                 "  "                      600                                                                               ##STR228##       H            "                 "  "                      601                                                                              "                 CH.sub.3     "                 "  "                      602                                                                               ##STR229##       H            CH.sub.3          CH CN                     603                                                                              "                 CH.sub.3     "                 "  "                      604                                                                               ##STR230##       H            "                 "  "                      605                                                                              "                 CH.sub.3     "                 "  "                      606                                                                               ##STR231##       H            "                 "  "                      607                                                                              "                 CH.sub.3     "                 "  "                      608                                                                               ##STR232##       H            "                 "  "                      609                                                                              "                 CH.sub.3     "                 "  "                      610                                                                               ##STR233##       H            "                 "  "                      611                                                                              "                 CH.sub.3     "                 "  "                      612                                                                               ##STR234##       H            "                 "  "                      613                                                                              "                 CH.sub.3     "                 "  "                      614                                                                               ##STR235##       H            CH.sub.3          CH CN                     615                                                                              "                 CH.sub.3     "                 "  "                      616                                                                               ##STR236##       H            "                 "  "                      617                                                                              "                 CH.sub.3     "                 "  "                      618                                                                               ##STR237##       H            "                 "  "                      619                                                                              "                 CH.sub.3     "                 "  "                      620                                                                               ##STR238##       H            "                 "  "                      621                                                                              "                 CH.sub.3     "                 "  "                      622                                                                               ##STR239##       H            "                 "  "                      623                                                                              "                 CH.sub.3     "                 "  "                      624                                                                               ##STR240##       H            CH.sub.3          CH CN                     625                                                                              "                 CH.sub.3     "                 "  "                      626                                                                               ##STR241##       H            "                 "  "                      627                                                                              "                 CH.sub.3     "                 "  "                      628                                                                               ##STR242##       H            "                 "  "                      629                                                                              "                 CH.sub.3     "                 "  "                      630                                                                               ##STR243##       H            "                 "  "                      631                                                                              "                 CH.sub.3     "                 "  "                      632                                                                               ##STR244##       H            "                 "  "                      633                                                                              "                 CH.sub.3     "                 "  "                      634                                                                               ##STR245##       H            "                 "  "                      635                                                                               ##STR246##       CH.sub.3     CH.sub.3          CH CN                     636                                                                               ##STR247##       H            "                 "  "                      637                                                                              "                 CH.sub.3     "                 "  "                      638                                                                               ##STR248##       H            "                 "  "                      639                                                                              "                 CH.sub.3     "                 "  "                      640                                                                               ##STR249##       H            "                 "  "                      641                                                                              "                 CH.sub.3     "                 "  "                      642                                                                               ##STR250##       H            "                 "  "                      643                                                                              "                 CH.sub.3     "                 "  "                      644                                                                               ##STR251##       H            CH.sub.3          CH CN                     645                                                                              "                 CH.sub.3     "                 "  "                      646                                                                               ##STR252##       H            "                 "  "                      647                                                                              "                 CH.sub.3     "                 "  "                      648                                                                               ##STR253##       H            "                 "  "                      649                                                                              "                 CH.sub.3     "                 "  "                      650                                                                              "                 "            C.sub.2 H.sub.5   "  "                      651                                                                              "                 C.sub.2 H.sub.5                                                                            CH.sub.3          "  "                      652                                                                               ##STR254##       H            CH.sub.3          CH CN                     653                                                                              "                 CH.sub.3     "                 "  "                      654                                                                               ##STR255##       H            "                 "  "                      655                                                                              "                 CH.sub.3     "                 "  "                      656                                                                               ##STR256##       H            "                 "  "                      657                                                                              "                 CH.sub.3     "                 "  "                      658                                                                               ##STR257##       H            "                 "  "                      659                                                                              "                 CH.sub.3     "                 "  "                      660                                                                               ##STR258##       H            "                 "  "                      661                                                                              "                 CH.sub.3     "                 "  "                      662                                                                               ##STR259##       H            "                 "  "                      663                                                                              "                 CH.sub.3     "                 "  "                      664                                                                               ##STR260##       H            H                 CH CN                     665                                                                              "                 "            CH.sub.3          "  "                      666                                                                              "                 "            CH.sub.2 Cl       "  "                      667                                                                              "                 "            C.sub.2 H.sub.5   "  "                      668                                                                              "                 "            C.sub.3 H.sub.7 (i)                                                                             "  "                      669                                                                              "                 "            C.sub.4 H.sub.9 (t)                                                                             "  "                      670                                                                              "                 CH.sub.3     H                 "  "                      671                                                                              "                 "            CH.sub.3          "  "                      672                                                                              "                 "            CH.sub.2 Cl       "  "                      673                                                                              "                 "            C.sub.2 H.sub.5   "  "                      674                                                                              "                 "                                                                                           ##STR261##       "  "                      675                                                                               ##STR262##       CH.sub.3     C.sub.3 H.sub.7 (i)                                                                             CH CN                     676                                                                              "                 "            C.sub.4 H.sub.9 (t)                                                                             "  "                      677                                                                              "                 C.sub.2 H.sub.5                                                                            H                 "  "                      678                                                                              "                 "            CH.sub.3          "  "                      679                                                                              "                 "            C.sub.2 H.sub.5   "  "                      680                                                                              "                                                                                                ##STR263##  H                 "  "                      681                                                                              "                 "            CH.sub.3          "  "                      682                                                                              "                 "            C.sub.2 H.sub.5   "  "                      683                                                                              "                 COCH.sub.3   H                 "  "                      684                                                                              "                 "            CH.sub.3          "  "                      685                                                                              "                 "            C.sub.2 H.sub.5   "  "                      686                                                                              "                 SO.sub.2 CH.sub.3                                                                          H                 "  "                      687                                                                               ##STR264##       SO.sub.2 CH.sub.3                                                                          CH.sub.3          CH CN                     688                                                                              "                 "            C.sub.2 H.sub.5   "  "                      __________________________________________________________________________     *1 .sup.1 HNMR(CDCl.sub.3) δ; ppm 3.32(s, 3H), 4.63(s, 2H), 7.37(d,     1H), 7.62(dd, 1H), 8.37(d, 1H)                                           

The compounds of this invention exhibit high insecticidal activitiesagainst various species of insect pests such as cutworms, diamondbackmoth, aphids, leafhoppers and planthoppers. In recent years the decreaseof the control effects of organophosphorus and carbamate insecticides,which is caused by the development of resistance to these insecticides,has become serious problem. In such situations, the development of newinsecticides which is effective on the resistant pests has been desired.The compounds of this invention possess superior insecticidal activitiesagainst not only susceptible strains but also resistant ones.

The insecticides covered by this invention contain as active ingredientsone or more types of the compounds as expressed by the general formula(1). These active ingredients, may be used as produced but normally theyare used in any of the forms which ordinary agricultural chemicals cantake, namely wettable powder, dust, emulsifiable concentrate, suspensionconcentrates, smoking chemicals, fumigant, granule, or otherformulations. For additives and carriers are used soybean flour, wheatflour or other vegetable flours, diatomaceous earth, apatite, gypsum,talc, pyrophyllite, clay or other fine mineral powders, when solidformulations are intended.

When liquid formulations are intended, then for solvents are usedkerosene, mineral oil, petroleum, solvent naphtha, xylene, cyclohexane,cyclohexanone, dimethylformamide, dimethylsulfoxide, alcohol, acetone,water, etc. A surface active agent may, if necessary, be added in orderto give a homogeneous and suitable formulation. The wettable powders,emulsifiable concentrates, suspension concentrates, etc. thus obtainedare diluted with water into suspensions or emulsions of a prescribedconcentration, before they are actually sprayed on plants in the field.In the case of dusts or granules, they are directly applied withoutfurther processing.

It goes without saying that the compound(s) of this invention iseffective even alone, but it can be used by mixing with various types ofinsecticides, acaricides and fungicides.

Typical examples of acaricides and insecticides which can be used bymixing with the compounds of this invention are described below:

Acaricides (fungicides): chlorobenzilate, chloropropylate, proclonol,bromopropylate, dicofol, dinobuton, binapacryl, chlordimeform, amitraz,propargite, PPPS, benzoximate, hexythiazox, fenbutatin oxide,polynactine, chinomethionat, thioquinox, chlorfenson, tetradifon,phenproxide, avermectins, clofentezine, flubenzimine, fenazaquin,pyridaben, fenproximate, chlorfenethol, thiophanate-methyl, benomyl,thiram, iprobenfos, edifenfos, fthalide, probenazole, isoprothiolane,chorothalonil, captan, polyoxin-B, blasticidin-S, kasugamycin,validamycin, tricyclazole, pyroquilon, phenazine oxide, mepronil,flutolanil, pencycuron, iprodione, hymexazole, metalaxyl, triflumizole,diclomezine, tecloftalam, vinclozolin, procymidone, bitertanol,triadimefon, prochloraz, pyrifenox, fenarimal, fenpropimorph, triforine,metalaxyl, oxycarboxin, pefrazoate, diclomedine, fluazinam, oxadixyl,ethoquinolac, TPTH, propamocarb, fosetyl, dihydrostreptomycin,anilazine, dithianon, diethofencarb. Organophosphorus-type andcarbamate-type insecticides (acaridides): fenthion, fenitrothion,diazinon, chlorpyrifos, oxydeprofos, vamidothion, phenthoate,dimethoate, formothion, malathion, trichlorfon, thiometon, phosmet,menazon, dichlorvos, acephate, EPBP, dialifos, parathion-methyl,oxydemeton-methyl, ethion, aldicarb, propoxur, methomyl, fenobucarb,BPMC, pyraclofos, monocrotophos, salithion, cartap, carbosulfancarbofuran, benfuracarb, metolcarb, carbaryl, pirimicarb, ethiofencarb,fenoxycarb,

Pyrethroide-type insecticides (acaricides): permethrin, cypermethrin,deltamethrin, fenvalerate, fenpropathrin, pyrethrins, allethrin,tetramethrin, resmethrin, parthrin, dimethrin, proparthrin, bifenthrin,prothrin, fluvalinate, cyfluthrin, cyhalothrin, flucythrinate,ethofenprox, cycloprothrin, tralomethrin, silaneophan.Benzoylphenylurea-type and other types insecticides: diflubenzuron,chlorfluazuron, triflumuron, teflubenzuron, buprofezin, pyriproxyfen,flufenoxuron, Machine oil.

Same examples of the formulations are given below. The carriers,surface-active agents, etc. that are added, however, are not limited tothese Examples.

EXAMPLE 7 Emulsifiable concentrate

    ______________________________________                                        The compound of this invention                                                                      10 parts                                                Alkylphenyl polyoxyethylene                                                                          5 parts                                                Dimethyl formamide    50 parts                                                Xylene                35 parts                                                ______________________________________                                    

These components are mixed and dissolved and, for use in spraying, theliquid mixture is water-diluted into an emulsion.

EXAMPLE 8 Wettable powder

    ______________________________________                                        The compound of this invention                                                                      20 parts                                                Higher alcohol sulfuric ester                                                                        5 parts                                                Diatomaceous earth    70 parts                                                Silica                 5 parts                                                ______________________________________                                    

These components are mixed and ground to fine powder, which for use inspraying, are water-diluted into a suspension.

EXAMPLE 9 Dust

    ______________________________________                                        The compound of this invention                                                                         5 parts                                              Talc                     94.7 parts                                           Silica                   0.3 parts                                            ______________________________________                                    

These are mixed and ground and used as-ground in spraying.

EXAMPLE 10 Granule

    ______________________________________                                        The compound of this invention                                                                          5 parts                                             Clay                     73 parts                                             Bentonite                20 parats                                            Sodium dioctylsulfosuccinate                                                                            1 part                                              Sodium phosphate          1 part                                              ______________________________________                                    

The above compounds are granulated, and applied as it is when used.

Industrial applicability

The tests below show the insecticidal activity of the compounds of thisinvention.

TEST 1 Efficacy for cotton aphid

30 to 50 insects of cotton aphid per plot were inoculated using a smallbrush on cucumber leaves which were seeded in pots, 10 cm in diameter,and 10 days old after germination. A day later, wounded insect pestswere removed, and a chemical solution, which was prepared in the waythat the emulsifiable concentrate described in Example 7 of the aboveexample of insecticide was diluted with water to 125 ppm of compoundconcentration according to the prescription, was sprayed. The pots wereplaced in a thermostatic room at temperature of 25° C. and humidity of65%. The number of survival pests was counted 7 days later and thecontrol efficacy was calculated by comparing with that of untreatedplot. The results are shown in Table 2.

                  TABLE 2                                                         ______________________________________                                                             Control Efficacy (7 days later)                          Compound No.   125 ppm                                                        ______________________________________                                         1              100%                                                           2             100                                                             3             100                                                             4             100                                                             6             100                                                             8             100                                                             10            100                                                             16            100                                                             20            100                                                             21            100                                                             22            100                                                             23            100                                                             24            100                                                             25            100                                                             27            100                                                             29            100                                                             31            100                                                             32            100                                                             33            100                                                             38            100                                                             44            100                                                             48            100                                                             50            100                                                             51            100                                                             53            100                                                             57            100                                                             60            100                                                             62            100                                                             64            100                                                             66            100                                                             68            100                                                             70            100                                                             72            100                                                             73            100                                                             74            100                                                             78            100                                                             80            100                                                             82            100                                                             84            100                                                             86            100                                                             88            100                                                             92            100                                                             96            100                                                            100            100                                                            102            100                                                            115            100                                                            116            100                                                            120            100                                                            124            100                                                            130            100                                                            132            100                                                            136            100                                                            144            100                                                            145            100                                                            146            100                                                            148            100                                                            149            100                                                            150            100                                                            151            100                                                            152            100                                                            163            100                                                            164            100                                                            169            100                                                            170            100                                                            171            100                                                            172            100                                                            173            100                                                            174            100                                                            177            100                                                            178            100                                                            188            100                                                            189            100                                                            190            100                                                            194            100                                                            203            100                                                            206            100                                                            213            100                                                            236            100                                                            366            100                                                            368            100                                                            381            100                                                            383            100                                                            543            100                                                            Comparative compound A                                                                        27                                                            Comparative compound B                                                                       100                                                            ______________________________________                                         Comparative compound A:                                                       ##STR265##                                                                    Comparative compound B:                                                       ##STR266##                                                               

TEST 2 Efficacy for green rice leafhopper

Rice seedlings of 7 days old after germination were immersed in achemical solution, which was prepared in the way that the emulsifiableconcentrate described in Example 7 of the above example of insecticidewas diluted with water to 125 ppm of compound concentration according toprescription, for 30 seconds. After dried in air, the treated seedlingswere placed in test tubes and 10 insects of 3rd-instar larvae of greenrice leafhopper resistant to the organophosphorus and carbamateinsecticides were inoculated. The tubes were covered with gauze, andplaced in a thermostatic room at temperature of 25° C. and humidity of65%. The mortality was checked 5 days later. The results are shown inTable 3.

                  TABLE 3                                                         ______________________________________                                                              % mortality (5 days later)                              Compound No.     125 ppm                                                      ______________________________________                                         1                 100%                                                        2                100                                                          4                100                                                          6                100                                                          8                100                                                         10                100                                                         16                100                                                         18                100                                                         20                100                                                         21                100                                                         22                100                                                         23                100                                                         24                100                                                         25                100                                                         27                100                                                         28                100                                                         29                100                                                         31                100                                                         32                100                                                         33                100                                                         35                100                                                         36                100                                                         44                100                                                         48                100                                                         50                100                                                         51                100                                                         53                100                                                         57                100                                                         60                100                                                         62                100                                                         66                100                                                         68                100                                                         72                100                                                         73                100                                                         74                100                                                         78                100                                                         82                100                                                         84                100                                                         86                100                                                         88                100                                                         92                100                                                         96                100                                                         100               100                                                         102               100                                                         116               100                                                         120               100                                                         124               100                                                         130               100                                                         132               100                                                         136               100                                                         144               100                                                         146               100                                                         148               100                                                         150               100                                                         152               100                                                         164               100                                                         169               100                                                         170               100                                                         171               100                                                         172               100                                                         173               100                                                         174               100                                                         178               100                                                         188               100                                                         190               100                                                         201               100                                                         203               100                                                         213               100                                                         236               100                                                         366               100                                                         368               100                                                         369               100                                                         381               100                                                         Comparative Compound A                                                                           0                                                          Comparative Compound B                                                                           0                                                          Comparative Compound C                                                                           0                                                          ______________________________________                                         Comparative compound A and B: The same as test 1                              Compound C:                                                                   ##STR267##                                                               

TEST 3 Efficacy for rice armyworm

The test compounds were formulated into the wettable powder in the samemanner as Example 8. The compounds were diluted with water to 125 ppm. Amaize leaf was immersed in the chemical solution for 30 seconds. Afterair-dried, the treated leaf was placed in a petri dish and five3rd-instar larvae of rice armyworm were inoculated. The petri disheswere covered with glass lids, and placed in a thermostatic room at 25°C. and 65% relative humidity. The mortality was checked 5 days later.Two replications were conducted in the each test. The results are shownin Table 4.

                  TABLE 3                                                         ______________________________________                                                              % mortality (5 days later)                              Compound No.     125 ppm                                                      ______________________________________                                        21                 100%                                                       22                100                                                         23                100                                                         24                100                                                         25                100                                                         51                100                                                         57                100                                                         88                100                                                         92                100                                                         148               100                                                         172               100                                                         381               100                                                         Comparative compound A                                                                           0                                                          Comparative compound B                                                                           0                                                          Comparative compound D                                                                           40                                                         ______________________________________                                         Comparative compound A and B: The same as Test 1                              Compound D:                                                                   ##STR268##                                                               

We claim:
 1. An insecticidal compound of the formula ##STR269## whereinA completes a 5 or 6 membered aromatic ring having one heteroatomic ringmember comprising nitrogen, provided, however, that the ring is notunsubstituted 2-pyridyl;R₁ is hydrogen or C₁₋₅ alkyl; C₁₋₅ haloalkyl,C₁₋₅ alkoxy, C₁₋₅ alkylthio, C₁₋₅ alkylsulfonyl, cyano, halogen, or C₁₋₅dialkylamino; X is C₁₋₃ alkylene or C₁₋₃ alkylidene; R₂ is hydrogen,carbamoyl, monoalkylcarbamoyl, C₁₋₅ dialkylcarbamoyl, thiocarbamoyl,monoalkylthiocarbamoyl, sulfamoyl, monoalkylsulfamoyl, C₁₋₅dialkylsulfamoyl, C₁₋₅ alkyl, C₂₋₅ alkenyl, C₂₋₅ alkynyl, C₃₋₈cycloalkyl, C₃₋₈ cycloalkenyl, aryl, or the radical

    --Y--R.sub.5

whereinY is 0, S(O)_(n), CO, CS or CO₂, n is 0, 1 or 2, R₅ is hydrogen,C₁₋₅ alkyl, C₂₋₅ alkenyl, C₂₋₅ alkynyl, C₃₋₈ cycloalkyl, C₃₋₈cycloalkenyl, or aryl; R₃ is hydrogen, C₁₋₅ alkyl, C₂₋₅ alkenyl, C₂₋₅alkynyl, C₃₋₈ cycloalkyl, or C₃₋₈ cycloalkenyl; R₄ is cyano or nitro; Zis CH or N;and an insecticidal acceptable salt thereof.
 2. Aninsecticidal compound according to claim 1 wherein the aromatic ring isof the formula ##STR270## wherein A completes a 6 membered aromatic ringselected from the group pyridyl;R₁ is hydrogen or C₁₋₅ alkyl; C₁₋₅haloalkyl, C₁₋₅ alkoxy, C₁₋₅ alkylthio, C₁₋₅ alkylsulfonyl, cyano,halogen, or C₁₋₅ dialkylamino; X is C₁₋₃ alkylene or C₁₋₃ alkylidene; R₂is hydrogen, monoalkylcarbamoyl, C₁₋₅ dialkylcarbamoyl, C₁₋₅ alkyl, C₂₋₅alkenyl, C₂₋₅ alkynyl, C₃₋₆ cycloalkyl, aryl, or the radical

    --Y--R.sub.5

whereinY is O, CO, CO₂ or SO₂ ; R₅ is C₁₋₅ alkyl or aryl; R₃ ishydrogen, C₁₋₅ alkyl, or C₃₋₆ cycloalkyl; Z is N;and an insecticidalacceptable salt thereof. 3.N-cyano-N'-(2-chloro-5-pyridylmethyl)-N'-methylacetamidine. 4.2-(2-chloro-5-pyridylmethylamino)-1-nitro-1-butene. 5.N-cyano-N'-(2-chloro-5-pyridylmethyl)-N'-ethylacetamidine. 6.N-(2-chloro-5-pyridylmethyl)-N-methyl-N'-nitroacetamidine.
 7. Aninsecticidal composition comprising the compound of claim 2 as an activeingredient.
 8. An insecticidal composition comprising the compound ofclaim 3 as an active ingredient.
 9. An insecticidal compositioncomprising the compound of claim 4 as an active ingredient.
 10. Aninsecticidal composition comprising the compound of claim 5 as an activeingredient.
 11. Method of controlling both lepidopterous and hemipterousinsects by applying to the locus where control is desired aninsecticidally effective amount of a compound of claim
 1. 12. Method ofcontrolling both lepidopterous and hemipterous insects by applying tothe locus where control is desired an insecticidally effective amount ofa compound of claim
 2. 13. Method of controlling both lepidopterous andhemipterous insects by applying to the locus where control is desired aninsecticidally effective amount of the compound of claim
 3. 14. Methodof controlling both lepidopterous and hemipterous insects by applying tothe locus where control is desired an insecticidally effective amount ofthe compound of claim
 4. 15. Method of controlling both lepidopterousand hemipterous insects by applying to the locus where control isdesired an insecticidally effective amount of the compound of claim 5.16. Method of controlling both lepidopterous and hemipterous insects byapplying to the locus where control is desired an insecticidallyeffective amount of the compound of claim 6.